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21.
We present a method to build potential energy surfaces with the correct permutational symmetry of identical atoms. It is explained and applied to an A $_2$ B $_2$ molecular system. This method allows us to use different reference geometries, which are often needed in large molecules. 相似文献
22.
A method for calibration and validation subset partitioning 总被引:13,自引:0,他引:13
This paper proposes a new method to divide a pool of samples into calibration and validation subsets for multivariate modelling. The proposed method is of value for analytical applications involving complex matrices, in which the composition variability of real samples cannot be easily reproduced by optimized experimental designs. A stepwise procedure is employed to select samples according to their differences in both x (instrumental responses) and y (predicted parameter) spaces. The proposed technique is illustrated in a case study involving the prediction of three quality parameters (specific mass and distillation temperatures at which 10 and 90% of the sample has evaporated) of diesel by NIR spectrometry and PLS modelling. For comparison, PLS models are also constructed by full cross-validation, as well as by using the Kennard-Stone and random sampling methods for calibration and validation subset partitioning. The obtained models are compared in terms of prediction performance by employing an independent set of samples not used for calibration or validation. The results of F-tests at 95% confidence level reveal that the proposed technique may be an advantageous alternative to the other three strategies. 相似文献
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E. Lazzaro R. Coelho 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,19(1):97-101
A major limit to steady state and advanced high operation of tokamaks of reactor class is due to the onset of tearing modes that develop magnetic and may cause loss of energy confinement or a major disruption. Here the structure of a classical problem
about the effects of external control helical fields is analysed and it is shown to offer a general paradigm of response of
low order classical and neoclassical tearing modes to a wide class of external perturbations. New results of principle on
the structural stability of the response model are obtained, leading to a clear interpretation of the role of “seed islands"
in the onset of neo-classical tearing modes and the role of finite ion larmor radius corrections to Ohm's law.
Received 12 November 2001 and Received in final form 4 January 2002 相似文献
26.
Lejeune C Coelho C Bonhomme-Coury L Azaïs T Maquet J Bonhomme C 《Solid state nuclear magnetic resonance》2005,27(4):242-246
We show that it is possible to efficiently transfer magnetization from 31P to 29Si, using variable amplitude CP MAS experiment. This experiment is demonstrated by using Si5O(PO4)6, the synthesis protocol of which is described. From the obtained results, we show that the experiment allows the spectral edition of 29Si spectra from 31P→29Si CP, enabling the studies of derivatives involving Si–O–P linkages, such as phosphosilicate glasses, microporous silicoaluminophosphates (SAPO) and bioactive phosphosilicates. 相似文献
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Zaqueu Coelho 《Transactions of the American Mathematical Society》2004,356(11):4427-4445
For a minimal circle homeomorphism we study convergence in law of rescaled hitting time point process of an interval of length 0$">. Although the point process in the natural time scale never converges in law, we study all possible limits under a subsequence. The new feature is the fact that, for rotation numbers of unbounded type, there is a sequence going to zero exhibiting coexistence of two non-trivial asymptotic limit point processes depending on the choice of time scales used when rescaling the point process. The phenomenon of loss of tightness of the first hitting time distribution is an indication of this coexistence behaviour. Moreover, tightness occurs if and only if the rotation number is of bounded type. Therefore tightness of time distributions is an intrinsic property of badly approximable irrational rotation numbers.
29.
Coelho CJ Galvão RK de Araújo MC Pimentel MF da Silva EC 《Journal of chemical information and computer sciences》2003,43(3):928-933
A novel strategy for the optimization of wavelet transforms with respect to the statistics of the data set in multivariate calibration problems is proposed. The optimization follows a linear semi-infinite programming formulation, which does not display local maxima problems and can be reproducibly solved with modest computational effort. After the optimization, a variable selection algorithm is employed to choose a subset of wavelet coefficients with minimal collinearity. The selection allows the building of a calibration model by direct multiple linear regression on the wavelet coefficients. In an illustrative application involving the simultaneous determination of Mn, Mo, Cr, Ni, and Fe in steel samples by ICP-AES, the proposed strategy yielded more accurate predictions than PCR, PLS, and nonoptimized wavelet regression. 相似文献